Aluminum-chloride process



l Oct 25 927 H. LEA ET AL ALUMINUM CHLDRIDE PROCESS Original Filed June 20. 1925 3 Sheets-Sheet 1 impr/zeg,

1,646,732 H. I. LEA ET AL ALUMINUM CHLORIDE PROCESS original Filed June 20. 1923 3 Sheets-Sheet 2 fin/(wier Oct. 25. 1927.

l 1,646,732 oct. 25,1927. H L LEA ET AL ALUMINUM CHLORIDE PROCES S original Filed June 2o, 192s s sheets-sheet 3 f War/Zay.

i atented Oct.` 25, 1927.

UNITED STATES PATENT OFFICE.

HINBY I. LEA., OF SANTA MONICA, CALIFORNIA, AND CLIFFORD W. HUMPHREY, OF

BED BANK, NEW JERSEY.

ALUMINUM-CHLORIDE PROCESS.

Application tiled June 20, 1923, 'Serial No. 646,555. Renewed Mai-c1116, 1927.

This .invention relates to processes for the production, principally of aluminum' nets of some value. Consequently, although ways and means of treating aluminum chloride is thel most valuable product of the process at present, and although for that reason we term our recess one for producing aluminum chlori e, xt is not to be understood that it may-not an object, or. perhaps under other conditions the rincipal object, to roduce one or more iie other products o the process.

There are various procedures, differing somewhat from eachother, by which our process may be carried out; and the process as a whole will be best .understood from the following detailed descriptions of preferred methods, rather than from any general statement that we may make in advance. However, for the purpose of generally distinguishing the processes of the several applications.- from each other we will make a general and preliminary statement of the distinguishing features of the several variations. It will be understood, nevertheless, that this statement is not intended in the least as a restriction or limitation upon the invention, either as' a whole or as to the s eciiic aspects herein claimed, but is intende only to give a clear idea of the lines of demarkation between the several specific variations of the fundamental process and as between the specific claims of the several copending applications.

This application is 1n part a divisional continuation of our application .on aluminum chloride process, filed May '31, 1922, Serial Number 564,762. In that ap lication we .have described a process inc uding steps that may be said, in a broad way, to amount to the chlorination of a more or less dehydrated or a more or less dehydrated and decomposed aluminum sulphate; and the specific variations in the methods have to do with various ways and means of effecting `successive operations; as for instance the ways and means of obtaining the chlorine for the chlorinating reaction or the specific the original aluminum sulphate, as to whether it is decomposed or not, before being chlorinated.

When we refer herein to aluminum sulphate, it will be understood that we include that substance in whatever form itmay be used. For instance it may be in ores that carry the sulphate in such associations that the ores themselves may be put directly into vour process; or it may be in ores that require .pre-treatment to separate certain other matters; or it may be in ores that may be -put directly into the process and that may require one or two additional steps during the process. Such for instance is the ore alunite, an aluminum and potassium lsulhate ore; and how alunite may be treated is hereinafter set out.

A typical form of the general process may, for the purposes of this preliminary general statement, he described as follows: We take an aluminum sulphate or an aluminum sulphate Acarrying ore, and if it has not been previously dehydrated, we first dehydrate it. Thenl by application of 'suitabletemperature we decompose the sulphate into aluminum oxide and arsulphur and oxygen compound or compounds. For instance the sulphur and oxygen may either come off as SOa or as SO2 Aplus O. Then we chlorinate that oxide that: we have obtainedl by decomposing the sulphate. Just how and where the chlorine is preferably obtained, in thecompletel process, we will advert to later; as different methods of obtaining the chlorine, or diierent methods of chlorination, form some of the variations that are covered in the various applications. The chlorination is carried by subjecting the oxide, under a suitable temperature, to the action of chlorine in the presence of carbon. The chlorine ma be, and preferably is, in most variations o this process, free c lorine; but, as we will set out, the chlorination step may be carried on without theA necessity' of first obtaining free chlorine.. This will beV adverted to later. Whatever maybe the immediate chlorinating agency chlorination, carried on in the pres.

i carbon, is preferahlycarried on in the presence of hydrocarbon, in the manner and 'with the resulting advantages as here` inafter explained. The process, m itself, of

chlorinat analuminum oxide or,an alu- L minum oxi ercarryingore, in the presence matter of the claims of said prior applicaapplication A This present applicationr which iyill be identified' as applicationJB,

has its claims'direeted characteristically tothe chlorination of aluminum oxide that has been produced 'by'decompos'itlon of a. Sulphate or itsl equivalent; andalso the comin the presence of hydrocarbon.-

original sulp ate;` or fof vc lilorinating. the 'sulphate directly, withou't f irstgdecomposing it; or decomposing it simultaneously :with

mentioned having issued 1as.,i Patents N 1.55am: ma io'ctiabere, 1925, 'and 15546;-,

j2ee, dated Jury '14 1925; V0g Suche matters we therefore no no t'specifiallyhefref` treat: the .flescription here fhing' directed an oxidcf'obtainedh decompositionoit,he

sulphate. lis Chlor-in ted. But `itfu'ill not,

-ihcrghy lie laken that-fthe-.-lnetli'oth here del-i scribed limited to the fspecfic details stated.. except as sojspeciically 'limited -gby' .the appended claims.

and soit is only for thepurposeof clarify- 7 ing "the follouing detailed descriptionsthat we illustrate a suitable apparatus in the-ac companyin'g drawings. "5I-n theserdrawings: there is a diagram which, for convenience of illustration` istlividedinto several figuresl as Fig.; 1?, Fig. 1 ,rFigL' lc, Fig. 1"; and'Fig.-

i! is a section shoivingia sform of chloride' herein 'exp'ained condcnsin" chamber that ,uff/wdr arid which may lic hereinafter referred t0` as method No. l. we take aluminum Sulphate',-

aml. placing it iu a retort 1 0'heat'itt'o a tcmperature sulliccnt. to drive olf' its vwater iii fr vstalliation; so thatnvc have the reaction:

mum amount of water4 may be driven o', .be-` anse the sulphate does not always -conta'in the maximum amount; Iandalso ,be'c'z1u.seit may be that this reaction', like others in tlie process may sometimes not go,thlr0 Agli't alisolute eompletionL-This willlvbe genera y understood in ing. f l

The product here is a dehydrated aluminum sul hate that 'may'A be -remo'ired from time to` ime' or preferably left in' the re- Il Y theA cooler lf2 efficient. temperature with air that throlg'h its air jacket 21; vand the heated air t atcome's ot't` the catal 'zerimav b connection xyithaIl-the -follow- 3 w e used torts for the nxtfrdecoinposition reaction.

The retortslO may be arranged" singly,l in` pairs, or more Vin a set so asV to provide for vrnore or lessjcontinuous operat'lon.- The water vapor that passes off goes through "pip 9 into"condense`r 13 or'may go directly ttl-atmosphere., y

Further application of heat Vto the dehy into aluminum; oigide, sulphur dioxide and oitygen (orv the aluniiriurn'o'xide/angl sulphur trioxide as hereinafteneplainecllaf follow# 'andjfft-hez extent` :of: decomposition.4 desired.

\Ye;.tind that-alisolutelryfull Vdecomposititm isiiot necessary*onpraetically desired Vthe time element, fthe, pressure. (above. -or .be-

this operationfpassrthroughthe' pipe 1l to which may b e here an-air or watercooleri l l1ihe' oxide may be removed .from tiureto Ytime-to .put inthe chlorinati; inglretortg'- 4or 'chlorination', as' hereinafter As will .bcv readilyunderstood, our processmaybe carried on in any suitable apparatus;

drying medium; l'may be sprayed down from theV to'pA and the gases next are drawn out by,` an exliauster 16l and passed'through a pipe 17 into `acatalyzer.18. t the same time this exhuster. draws in atmosphericair through 'aivalye controlled pipe 19, the air passing'throiigh awasher 20;'to cleanse and dr'y -it.` Cat-alyzer 18 is` preferably ofthe In this catalyzer th`e uncon'ibined sulphur Vdioxide an'd oxygenfare combined toform sulphur trioxide according to:

8151. plus 30 plus catalyzer equals 3. i. Theoxygen theoretically required f or this reaction may-be fully supplied by the oxygen from the lstl proceeding reaction; but we tiid"itha t' a"ri eirc'ess of oxygen (supplied here bythealr) xnakes'the reaction go onmore at any'comie'nient place in'the process, for

` `cool ig to maintain t s temperature.

From the catalyzer 18 the sulphur trioxide passes through pipe 22 to another cooler-23 which may be either air or water cooled. We may state here that wherever a cooler is used in this rocess it may-.be desirable to use an air cocer as we thereby can more readily use the heat in the furnaces. From the cooler the sulphur trioxide passesthro' h pipe 9A into an absorption tower 25. Inuthe absorption tower the gases "ass upwardly and sulphurlc acid is spray downwardly;

with the result that fuming s ulphuric acid is formed, and this sulphuric acid collecting in the bottom 'of the' tower asses out through pipe 26 into a 'storage chamber 27 to which water may be controllably fed through 27 to change the uming sulphuric into ordinary sulphuric of 66 B. gravity.

These-reactions are thus represented: (if Y they go to completion) BSO3 lus 3H2SO4 equals 3H S201 sans, plus 33,0 equals elizso.

Half this sulphuric acid is put back into absorption tower 25, thus'leaving half the' sulphuric acid 3H2SO,) in 27. Thus the summation of t esetwo reactions may be written: l

IV. 3SO3 plus SHZO equals 311250,.

If conditions in retort 10 have beenlsuc as to produceSO3 instead of SOz and O, or to partially produce S03, then thatl SO, will, with sulphuric acid in 15, become HZS2 0,. If SO3 is produced entirely in retort 10, then catalyzer 18 and cooler 23 and absorption tower 25 can be dispensed with; the H2320, going directly from 15 to 27. Y

Then into a retort or saltcake pan 30 that is heated to about the same temperature as `the first retort We introduce an alkali chloride, for instance, sodium chloride, and the sulphuric acid, in proper proportions for the followin reaction which then takes Iplace:

V. 3 2SC, plus NaCl-equals 3 a2 SO, plus (SHCI.

In this operation the chloride of sodium, potassium, calcium, magnesium or manganese may be used. If we use sodium chloride the result of this operation is to produce sodium sulphate and hydrochloric acid. -The sodium. sulphateis left in the retorts until the 4charge is exhausted `While the hydrochloric acid gas passes through pipe 31 into a drying chamber 3,2. This drying chamber may be ofbrick construction, filled with coke. The dried hydrochloric acid vapor then )asses-throu h pipe 33 into a heater 34. `This heater may e heated with waste gases from theretorts. Then the dry heated HCl gas passes through pipe 35 to the .secondcatalyzer 36 charged with broken brick, coke,

pumice stone, or other suitable material well soaked with a. solution of CuCl2 or other suitthe following takes able catalyzing material. This catalyzer 36 1s kept at a. temperature of about 450 C., and .also there is su pliedto this catalyzer. a suitable amount oi) air or oxygen so that lace: VI. 6HC1 plus 35 plus catalyzer equals 3H2O plus GCI.

Thel vapors and ,gases pass off through a pipe. 37 which has a chidensation bend 38 where the water is condensed and any remaining HCl is thus, taken off' in' .solution and then the chlorine gas passes through pipe 39 into a tower 40. This is a wooden tower lined with-lead and filled with coke, and s rayed with water to cleanse the gases and a sorb any remaining HCL Thence the gases pass through pipe 41 intoasimilar itower 42'.which is sprayed with sulphuric acid to dry the gases. Thence the gases are lead to a retort 43 which -is Vheated by any suitable means to`a temperature of about red heat, (say aboutv 600 C. or more). And into this retort is also introduced carbon and the A1O3 that has been produced in retoigts 10 when the dehydrated aluminum sulphate has been broken'up by heat. The carbon and Al,O,are ground and thoroughly mixed to give intimate contact and lbriquetted if found desirabl'e to prevent being carried over mechanically into the condensing chamber. Thefollowing reaction then takes place I VII. A120a plus 3C plus 6Cl plus heat equals A1201., plus 3CO.`

The result lis the production of carbon monoxide gas and anhydrous aluminum Achloride in vapor form. This aluminum chloride as fume passes into a sublimating chamtrol its final physical form; and in Fig. 2 we 11o have 'shown one form of apparatus suitable for that purpose. The chloride vapors from retort 43 enter a chamber 56 through pipe 55. This chamber has a brick top 51 heated by a heating jacket 52 receiving waste gases 115 from combustion under the retort, and whose temperature may be controlled by any suitable damper arrangement, for instance. The conical bottom 50 of chamber 56 is steam jacketed at 57, steam (or other vapor) being admitted at 58 and exhausted through a trap at 59. By controlling the pressure any selected temperature may be maintainedv atthe conical floor of chamber 56. A revoluble scraper 60 serves to scrape the chloride oil 125 floor 50 to drop through outlet 62 into re ceiver 63. The residual gases (CO) pass out through 14. Cool inert gases for instance, C0 or N) may be introduced at 65. The various operations follow: 1:0

(a) Pass cool gas through 52, air cool the jacket 5T and introduce cool gas at 65, and tht-n all or practically all the chloride will he sublimatcd in finely divided form.

(b) Heat top of chamber so that inside temperature is above the-boilingpoint of the huhu-idc, which is about 183 C. Floor 50 maintained slightl below' the melting point t 178 C.) and then the major portion of the chloride will be thrown down as a vvrvstal.

'The dei im above described also forms one nwans for obtaining fractional-condensation separation of certain final products of cer- 'tain methods herein described. -For in,v

stance'. where aluminum chloride and certain sulphurl compounds are final products, they may be at least partially separated by maintaining the proper temperatures in the chamher, its roof and floor; or, of course, they may be separated in any of thc-well known rictional condensation-systems.

Summing up this method it will be seen that we use as initial materials aluminum sulphate or sulphate bearing ores, etc.

(Equation I); sodium chloride (Equation V) and carbon (Equation VII.) Thedultim te. productsare sodium sulphate'(Equa-. tion V); aluminum chloride (Equatidn VII) and carbon "monoxidef uation VII). The ultimate thing that isv one is 'the chlorination 'of the oxide obtained by' dehydrating and decomposing aluminumA sulphate. In the particular procedure de= scribed we obtain the chlorine for the chlorination from hydrochloric Yacid which in tum is formed from sulphuric acidand sodium chloride, `and the-sulphuric acid -is formed from the sulphur dioxide and 'oxy gen (and/orSOs) that are driven'ot when the aluminum sulphate is reduced to aluminum oxide; and these particular things, with their varia tions form more particularly the subject matte'r of application C, hereinabove identified. HoweverV as such variations may form a part of the process as practically carried out, We mention typical ones. For instance, we have found that ifan atmosphere of SO3 is maintained in the initial retort- 10 and held under a suitable pressure (we have found a pressure of `about twelve pounds above atmosphere to be sullicient' at the temperature We have employed) then, instead-of the product being aluminum oxide and sulphur dioxide and oxygen. the product isaluminum oxide` and SO, (a temperature of about red heat is maintained and the pressure keeps the SOs from breaking up). Under these conditions the next operation (Equation III) may'be dispensed with; and the SO, may then immediately he `put into the operationrepresented by Equation 'IV to form sulphuric acid as has been touched upon before; or the SO, thus formed may be put directly into the operation represeiitedxby 'Equation V, into retort 30 along with the sodium chloride and water to form sodium sulphate and hydrochloric acid. Furthermore, it is possible here to dispense with the water and 70' thus' to obtain sodium' sulphite andchlorine direct instead of sodium sulphate and HCl and thus the next step (Equation IV) and the step of Equation VI" may be dispensed with.

Generally s peakingfwe iiid that Aas' our process involves the chlorination of aluminum oxide obtained,bydecomposition of dehydraedaluminum sulphate, we can ca on'thc operations at much/ lower tempera- .gb

tures than any other process of which we are aware; and we find also thatvsuch decomposed sulphatc lends itself very readily-t easy` chlorination. It will .be understood that in all forms of our process, anhydrous g5 aluminum sulphate may be the starting point of our actual operations; the sulphate may be dehydrated previously.'

nieuwe e.

u the aluminum sulphate in the savxneinan n eras before described; 'A I.' A1,(SO,),.18H,O plii'slieat equals 3S0,p'lus 30 (or equals A122), plus BSOnl Then as the next step we introduce the l.sulphur dioxide, and oxygen'gases, with or:

without extra oxygen,- and water (steam) 10o and thesodium chloride into a heating chamvber (such for instanceas shown at`30) withi the `result of formin `hydrochloric acid and sodium sul hate as ollows:

III, 3 O, plus 30 air plus BH2() 105 vplusV heat"pl us NaCl equals'vGHCl plus 3Na,SO,.

' This b'rin us to the same point as at the end of nation V in Method 1.v

The remaining operations are the saine as 110 operated, as previously described, to produce 125 trioxide. `These variations are, more specifically, the subject matter of the ap hcation Serial No. 646,556, Patent o. 1,558,897, dated October 27,1925; although sulphur they also apply tothe process of chlorinating u@ In'this method we `dehydrat/el and` break.

ofthe aluminum sulphate plete reactions may be obtaine' I Method 3.

In Method 3 the'first step isthe same as before described:

The second step `however, involves putting the undecomposed aluminum sulphate ,directly into reaction with the sodium chloride andrwater (steam).

II. Al2 SO), plus GNaCl lus 3H,O equals Al2 lus NazSO, plus 6 Cl.

heat equals This secon step may be looked upon more J or less as being a combination of stops II and III* of the second method, as ithasthe same ultimate ends; that is, -the production of aluminum oxide, sodium sulphate, and hydrochloric acid. This reaction (II) is `carried on a retort, such as 30, heated to about the temperature hereinbefore stated.

" Ihe A120, and NazSO4 are separated by lixiviation and the oxide dried.

Then the last two steps. VI. GHCl plus air BNZO plus 6Cl and VII.A A1203 plus 6Cl plus 3C equals Al,Cl,` plus 3CO are the saine as the last two steps in the other two methods.

Here again we have another variation in what we may term the intermediate process plus catalyzer equals `for getting the hydrochloric acid which is to provide the chlorine for chlorination of the aluminum oxide. This variation of the intermediate steps to produce the chlorinating agent, characterized by the specific decomposition of the sulphate in the same reaction in which the chlorinating agency is `formed, although coming generally u`nder the features of this present application because the sulphate is decomposed before chlorination, is specifically the subject matter of the identified application Serial No. 646,559. There are further variations of this intermediate process that" will further appear.

Further, with regard to any of the methods here explained, the carbon may be introduced to the system in retort 10 instead of' in the last retort, and may, in any case, be introduced in gaseous, liquid or solid form. Aftcr the sulphate has been decomposed it may he spraved with hydrocarbons. in any retort and thereby impregnated with carbonaceous matter, or the oxide may be sprayed with oil vapors, are retort being kept hot enoug)O to decom se the vapors and deposit car n. -Then t is impre ated oxide may be taken to retort 43 or't e last reaction may, if desired, be carried on in retort l0 by introducing the chlorine there.

If the oil or oil vapors aie introduced into the same retort that the chlorine is subsemay -be carried on there in any of the methods here described. And, the temperature' of theoxide in retort 10 being about the same as that required forehlorination,that'same temperature may be maintained, and the carbon and chlorine introduced and chlorination accom lishedwithout the necessity of reheating t e oxide. Wherever the last reaction' is carried' on the oxide ma be impregnated withcarbon as here escribed,

eaither previous to or during the introduction of chlorine. Furthermore, we may so impregnate the oxide with hydrocarbon liquids or vapors somewhat in excess of the chlorine reaction requirements and then the final chloride product will contain some lcondensed oil and be somewhat sticky andcokey and semi-liquid, less liable to deterioration, butnot at all objectionable for use in oil,

I distilling processes.

Although we thus prefer to luse hydrocarbons, to supply the carbon for the chlorination step; any form of carbon may be used, or any carbon carrying gas may be substi- 'tuted for hydrocarbon as or vapor, so far as the general aspect o our process lecon'- cerned.

-As an illustration of the application of this vprocess to original materials other than pure aluminum sulphate, we will give an' illustration of this application to alunite. It will be understood of course, from what wehave said, that the process may be applied to various ores that carry aluminum sulphate, together with other things whether; chemically combined with .the sulphate or not. Alunite is a good illustration of a material wherein the aluminum sulphate is chemically combined with other compounds.

The `formula, for alunite may be written:

I{,O,.A1,0,.4SO,.6H,O.

This ore is heated as hereinbefore'de-- Y scribed to such a temperature as to dehydrate it and as to drive off the SO3 content which inbefore referred to, there remains a substance that is made up and soluble potassium sulphate. The potasvarious manners liereinbefore described, by,

usingqthe .SO3 Acontent 'of 1th'e'original ore that has been driven olf in the decomposing operation. 1ti'ill'not be necessary'to go into the details of these steps-as theyfhave l been full -descrihed before.- Other charactcristic a uminuin and sulpliur'cai'ryin-g ores that may he used in' the processare Alunogen, A12O3-.3S0T11'8HQ Aluminite, AlgVOTSOIpfl-Hz() n wili be' miderstwdtim, although vc have here now stated various voriiis o f rooess, that' we have given these various'v orms Vby way of illustration onlyjfand that the process ma be variedin other mariners 'and still be wit in the scope of .the in'ye'ntion as expressed in the subjoined claims. Voi "i n stance, various combinationsor arrangements of the various `steps hereinkset :out may be made by selecting certainsteps from the one or more of the methods' herein stated and certain other steps from one onmoe of other methods herein stated; but it is Iunnecessary and would be burdensomeY to specifi'- cally state all of the possible-methods that might be `thus worked out.

Having described a preferred formof our invention, We claim: l

l. A process that includes dehydratin' and decomposing aluminum sulphateft'oy o tain aluminum oxide and thenchlo'rinating the resulting:r oxide to form anhydrous aluminuni'cliloridc.

9.. A process, that includes decomposing anhvdrous aluminum sulphate to obtain aluminum oxide and`then chlorinatin the resulting oxide to forni nhydrot a. uminum i carbon for the chloiinatintr action.

chloride.

3. A process that includes decomposing anhydrous aluminumsulphate with. heat to form aluminum oxide and 'then chlorinatingthe resulting oxide to form'anhydrous alu' ininum chloride. l

4. f .t process that includes decomposing alii of aluminum oxide A'aluminum 'sulphate and decomposin alu'ininuri'i oxide, 'then mixing the xi ewith 'carbonv by treating itwithhydrocarbon' to `impregnate it 'with carbcn'aceous matter, then 'then mixing the, resulting oxidcwith carbon andl treating,t the mixture with chlorine to forni anhydrous alumiiiuntchloride'.

(i. A .process-that includes decoi'nposiiigA aluminum sulphate to form aluminum oxide, then iiiipvegnating the resultingl oxide with carbon' iiiexcess ofthe amount requiredtfor chlorinatin, and thnchlorinating Ythe treated oxi `e to fornianhydrous aluminum chloride mixed -with` carbon.

. A process that includes decomposingaluminum sulphatef by heating to'forn'i aluminum o.\'ide,tlien cliloriirating thev oxide inthe presence -of carbon'at"atcinperature of about 600:' G or more to forni anhydrous aluminumchloride. A

8. A process thatnincludes decoir'iposing aluminum sulphate' to aluminum -oxide at a -temperature of about (300 C. or more,` -and then clilorin'atin'p,r the 'oxidein'th'e presence nl carbon fihile, holdi'pg the oxide at sub'- -st-.intiallv the same temperature.

4chlori'miting the so't'reated oxide.

, l'Osit process tltat includes dchydrating alumini'ui'i sulphate" and decomposingr it to aluminum oxide: then mixingV the oxide with carlion by treating it while heated with hydrocarbon -`to impregnato: it with carbonaeous iiiattei .`tlien cli-lorinating the .so lreatcd oxide.'

U11/A process that includes dehydi'iitingl aluminum sulphate and'deconiposing it to aluminum oxide. then mixingr the oxidcirith carbonby treating it with hydrocarbon to impregnateit ,irit-h carlifonaccous matter iii excess' of' the carbon required forcl'iloi'izia'tiiigl `then' 'clilo'iinatingr the vso 'treated oxide 'to'fo'rni anhydrous aluminum chloride inipregnated Withgtheexcess of h 'drocarbon,

12. 'A process that includes dehydrating aluminum sulphate' and decomposing it io aluminum oxide. then chlorinating the oxide in the presence of hydrocarbons to furnish ,In Vwitnessl that we claim the foregoing,r we have hereunto subscribed our names this 7thjday of June7 1923.

HENRY I. LEA.' vCLIFFORD YV. -HUMPHRE Y. 

